Composite materials

ABSTRACT

A mixed metal oxide material of tungsten and titanium is provided for use in a fuel cell. The material may comprise less than approximately 30 at. % tungsten. The mixed metal oxide may form the core of a core-shell composite material, used as a catalyst support, in which a catalyst such as platinum forms the shell. The catalyst may be applied as a single monolayer, or up to 20 monolayers.

This application is a National Stage application of International Application No. PCT/GB2014/050119, filed Jan. 16, 2014, which claims the benefit of United Kingdom Application No. 1300821.4, filed Jan. 16, 2013.

The present invention relates to materials for use in a fuel cell and particularly to core-shell composite materials for use in a fuel cell.

A fuel cell comprises an anode for oxidation of a fuel and a cathode where an oxidising agent, such as oxygen, is reduced. Ions are transported between the two electrodes by means of an electrolyte. Fuel supplied to the cell is oxidised at the anode, releasing electrons which pass through an external circuit to the cathode, where they are consumed during reduction of the oxidising species. In a polymer electrolyte membrane fuel cell (PEMFC), the fuel is usually hydrogen and the oxidising species is usually oxygen. A polymer electrolyte allows protons to flow from the anode to the cathode.

Platinum-containing catalysts are one of the most efficient catalysts for facilitating the oxygen reduction reaction (ORR) at the cathode of a fuel cell. Platinum, however, is a costly material and so methods for reducing the quantity of platinum required for an effective fuel cell are highly sought-after. Traditionally, platinum is dispersed over a carbon support to increase the surface area of the platinum, relative to its mass. A maximum in mass activity is produced with a platinum particle size of approximately 3-4 nm [References 1-4]. In this system, if the particle size of platinum is further reduced, oxygen reduction activity is also sharply reduced, limiting the advantages that can be achieved by dispersion. An additional disadvantage with the system is that the carbon support can become oxidised under fuel cell operating conditions. This oxidation leads to degradation of the catalyst, which limits the lifetime of the fuel cell [5].

Metal oxides have previously been investigated for use as fuel cell catalyst supports [6-18]. Metal oxides are less prone to oxidative corrosion than carbon, and can, therefore, be more stable in a fuel cell environment. The use of metal oxides as supports for fuel cell catalysts and methods of synthesising suitable oxides has been described in, for example, US2009/0065738A1, US2006/0263675, U.S. Pat. No. 7,704,918B2, US2007/0037041A1, WO2008/025751 and WO2009/152003 [14-18].

Core-shell catalysts with Pt as the shell material are reported in the literature [17-28]. A core-shell structure is represented schematically in FIG. 1. Many of the systems described in the literature contain a precious metal core, such as Au or Pd [19-22, 24-26, 28]. Consequently, although there is a potential reduction in the quantity of platinum required to produce an effective catalyst, use of another expensive metal within the core, keeps costs high. Other reported core materials include base metals (Cu in reference 27, for example), which are more cost-effective than platinum, but likely to be unstable in a fuel cell. Adzic et al [17, 18] disclose a core-shell type structure with a NaWO₃ core. WO2008/025751 [29] discloses a Pt-coated zirconia and cerium-doped zirconia core-shell system.

The present invention is based upon the determination that a mixed metal oxide based on tungsten combined with titanium can be used as a core supporting material. The loading of platinum at which bulk platinum like oxygen reduction behaviour is achieved has been identified by the present inventors. This is believed to be when discrete particles of platinum start to coalesce to form layers (i.e. a core-shell structure) and is evidenced by an overpotential for the oxygen reduction reaction equivalent to that seen for bulk platinum.

In particular, the inventors have found that when tungsten is added to a titanium oxide (also known as titania) support, the specific activity for oxygen reduction is increased at low platinum loadings. This suggests that the tungsten aids the wetting of the platinum onto the oxide surface allowing improved formation of core-shell structures.

The present inventors have also found that when the support is crystallised (to the anatase form of titanium oxide), the critical thickness (d_(crit)), at which bulk platinum like activity is achieved, is lowered—compared to a support comprising amorphous titanium oxide.

Accordingly, in its broadest aspect, the present invention provides a mixed metal oxide material of tungsten and titanium.

In a preferred embodiment, the mixed metal oxide material comprises less than approximately 30 atomic % tungsten (based on the total amount of metal, i.e. 30 at % W and 70 at % Ti).

Advantageously, the mixed metal oxide material comprises less than approximately 15 atomic % tungsten.

More advantageously, the mixed metal oxide material comprises from 6 to 11 atomic % tungsten, preferably between 7 and 9 atomic %.

Suitably, the mixed metal oxide material comprises titanium oxide doped with tungsten.

Suitably, the titanium oxide is crystalline, preferably the anatase form.

Another aspect of the present invention provides a catalyst support comprising a mixed metal oxide as described above.

A further aspect provides a catalytic medium comprising a mixed metal oxide material as described above and a catalyst applied to a surface of the mixed metal oxide material.

Preferably, the catalyst is applied as a catalytic layer to the mixed metal oxide material.

Preferably, the mixed metal oxide material is formed as a core particle.

Preferably, the core particle has a diameter of from 10-50 nm, more preferably 10-25 nm.

Ideally, the catalyst is applied as a shell on the core particle.

Alternatively, the mixed metal oxide material is formed as a layer structure.

In a preferred embodiment, the catalyst comprises platinum or platinum alloy.

Preferably, the catalyst comprises at least 1 ML (monolayer) of platinum or platinum alloy and 20 ML or fewer. More preferably, the catalyst comprises 14 ML or fewer of platinum or platinum alloy.

Another aspect of the present invention provides a method of producing a catalytic medium, the method comprising: forming a mixed metal oxide material as described above; and forming a catalytic layer comprising at least one monolayer of catalyst on the mixed metal oxide material.

Preferably the method comprises forming a catalytic layer of between 1 and 20 ML of platinum or platinum alloy.

More preferably, the catalytic layer is fewer than about 6 ML of catalyst.

A further aspect of the present invention provides a catalyst for a fuel cell, the catalyst comprising a mixed metal oxide material as described above.

The present invention also provides a fuel cell comprising a catalytic medium as described above.

A yet further aspect of the present invention provides use of a mixed metal oxide material as described above or a catalytic medium as described above in a fuel cell.

The term monolayer (ML) as used herein is used to mean the equivalent amount of catalytic material which would form a uniform layer of 1 atom thickness on a flat surface. It will be appreciated that, in practice, a surface of the mixed metal oxide is unlikely to be perfectly automatically flat. Accordingly, it will be understood that a 1 ML layer of catalyst on the mixed metal oxide substrate will have areas where there are a plurality of catalyst atoms in a layer and areas where there are no atoms of catalyst.

As used herein, the term mixed metal oxide indicates an oxide of a mixture of metals; a mixture of metal oxides; or a combination thereof.

FIG. 1 is a schematic cross-section of a core-shell structure and an equivalent layer structure used to model the core shell particle behavior;

FIG. 2 is a schematic representation of particle growth and nucleation onto supports with a low number of nucleation sites and an increased number of nucleation sites;

FIG. 3 is a schematic view of an electrochemical array substrate;

FIG. 4 is a chart showing the potential at which 1 μA raw current is reached during the oxygen reduction slow cycling experiment for Pt supported on amorphous and anatase titanium oxide. Error bars are plus and minus one standard deviation;

FIG. 5 is a chart showing the potential at which 3 μA raw current is reached during the oxygen reduction slow cycling experiment for amorphous and anatase titanium oxide. Error bars are plus and minus one standard deviation;

FIG. 6 is a chart showing an example O₂ reduction slow cycling CV for 0.7 ML of Pt supported on amorphous TiO_(x) indicating the two different potentials where ignition potentials have been compared; and

FIG. 7 is a chart showing the potential at which 1 μA raw current is reached during the oxygen reduction slow cycling experiment for Pt supported on anatase tungsten doped titanium oxide. Error bars are plus and minus one standard deviation.

For ease of reference, the mixed metal oxide of tungsten and titanium is represented as TiWO_(x). However, it will be appreciated that this is not a chemical formula indicating any specific stoichiometry, but merely a shorthand indication of the elemental composition of the material and is not to be taken as limiting on the stoichiometry of the material.

Thin film models of core-shell systems were produced with different platinum loadings and using titanium oxide supports with different crystallinity and varying levels of tungsten. The thin film models were tested for their activity towards the oxygen reduction reaction.

Thin film models of core-shell structures (see FIG. 1) with a tungsten-doped titanium oxide core and a platinum shell have been produced, which have the same (or similar) activity for oxygen reduction as bulk platinum. Traditionally, dopants have been added to metal oxides in order to increase conductivity by creating defects (such as oxygen vacancies). However, in addition to increased conductivity, dopants can also help to create defects on the surface of the metal oxides and therefore create more sites for nucleation of a metal overlayer. This would cause smaller particles to be formed and lead to a more complete metal film at a lower equivalent thickness (see FIG. 2). A film of platinum should approach the oxygen reduction capacity of bulk platinum, since a significant number of platinum atoms will be in contact.

Metal oxides also offer a stable alternative to carbon supports (which are prone to oxidative destruction) and would therefore increase the lifetime of fuel cells. One may also expect a more effective utilisation (activity per mass of platinum).

The inventors found that, as the loading of platinum was decreased on all of the support materials studied, the ignition potential (see below) for the oxygen reduction reaction initially remained constant. However, below a certain critical thickness (d_(crit)), the ignition potential (see below) started to decrease (i.e. the overpotential for the oxygen reduction reaction increases, or the electrodes are less active for the oxygen reduction reaction). At high loadings of platinum, the ignition potential was similar to a bulk platinum electrode. This suggests a core-shell model structure, where enough Pt atoms are in contact to behave as the bulk metal. As the platinum started to break into discrete particles, the ignition potential decreased.

The anatase form of titanium oxide allowed the loading of platinum to be reduced further than amorphous titanium oxide before the oxygen reduction behaviour shifted away from the bulk behaviour. This occurred below approximately 5 ML equivalent thickness of Pt.

The addition of tungsten to the anatase titanium oxide support showed evidence of improved activity at low loadings of platinum. This suggests that the tungsten aided the wetting of platinum onto the titanium oxide surface. That is to say, the results produced by the present inventors suggest that core-shell structures can be more easily formed when tungsten is present in the core.

EXAMPLE 1: SYNTHESIS OF SAMPLES

Thin film samples were deposited using a high-throughput PVD (Physical Vapour Deposition) system to model core-shell structures (see FIG. 1b ). The PVD system used is described in detail in reference 30. A range of oxide samples were synthesised onto different substrates including silicon wafers, quartz wafers and electrochemical arrays (10×10 arrays of gold contact pads as represented in FIG. 3). Titanium and tungsten were deposited from electron gun (E-gun) sources. The TiWO_(x) films were deposited in the presence of an atomic oxygen source (operating at 400 W power) with a pressure of approximately 5×10⁻⁵ Torr. These oxide films were heated in a tube furnace to 450° C. in the presence of oxygen. Such conditions allowed the anatase structure of the undoped titanium oxide to form and would lead to high oxygen stoichiometry materials.

The platinum was deposited onto the pre-deposited oxide thin films from an E-gun source. During deposition the oxide substrates were heated to 200° C. to dehydroxylate the surface. A shutter that was moved during deposition allowed different equivalent thicknesses of platinum to be deposited onto different fields. The amount of platinum deposited was calibrated by: depositing thicker films onto silicon substrates, measuring the thickness of the films by AFM (Atomic Force Microscopy), and producing a calibration curve against deposition time.

EXAMPLE 2: OXIDE CHARACTERISATION

The composition of the oxide films was determined using a Laser Ablation Inductively Coupled Plasma Mass Spectrometer (LA-ICP-MS, New Wave 213 nm laser & Perkin Elmer Elan 9000). This method gives the relative composition of the metallic elements, but is not capable of measuring the oxygen concentration. As the ICP-MS measurements are destructive, composition measurements were made on samples deposited onto silicon wafers. The same deposition conditions were then used to deposit onto equivalent electrochemical arrays.

X-Ray diffraction (XRD) patterns were obtained using the Bruker D8 Discover diffractometer, a powerful XRD tool with a high-precision, two-circle goniometer with independent stepper motors and optical encoders for the Theta and 2 Theta circles. The D8 diffractometer system is equipped with a GADDS detector operating at 45 kV and 0.65 mA. A high intensity X-ray IμS Incoatec source (with Cu Kα radiation) is incorporated allowing high intensity and collimated X-rays to be localised on thin film materials providing an efficient high throughput structural analysis. This analysis was carried out on oxide films deposited onto Si substrates.

EXAMPLE 3: ELECTROCHEMICAL SCREENING

The high-throughput electrochemical screening equipment enables electrochemical experiments on 100 independently addressable electrodes arranged in a 10×10 array in a parallel screening mode to be conducted. The equipment has been described in detail elsewhere [2, 31]. The geometric areas of the individual working electrodes on the electrochemical array are 1.0 mm².

The design of the cell and socket assembly provides a clean electrochemical environment with control of the temperature during experiments. In the experiments described, the temperature was maintained at 25° C. and a mercury/mercury sulphate (MMSE) reference electrode was used. The potential of the MMSE was measured vs. a hydrogen reference electrode prior to screening experiments and all potentials are quoted vs. the reversible hydrogen electrode (RHE). A Pt mesh counter electrode was used, in a glass compartment separated from the working electrode compartment by a glass frit. Various sweep rates were used for different experiments which are outlined in Table 1.

TABLE 1 Electrochemical screening procedure. Potential limits/ Sweep rate/ Experiment Gas V vs. RHE mV s⁻¹ Bubbling Ar 20 min 3 CVs in deoxygenated Ar above solution 0.025-1.200 100 solution O₂ saturation Bubbling Ar 60 s At 1.000 Bubbling O₂ At 1.000 10 min O₂ reduction steps Bubbling O₂ in Step from 1.00 to 0.60 solution and back to 1.00 in 50 mV increments every 90 s 3 CVs in O₂ saturated O₂ above solution 0.025-1.200 5 solution Bubbling Ar 20 min 200 CVs stability testing Ar above solution 0.025-1.200 100 Bubbling with O₂ for At 1.000 20 min 3 CVs in O₂ saturated O₂ above solution 0.025-1.200 5 solution O₂ reduction steps Bubbling O₂ in Step from 1.00 to 0.60 solution and back to 1.00 in 50 mV increments every 90 s Bubbling CO At 0.075 15 min Bubbling Ar At 0.075 20 min CO stripping Ar above solution 0.025-1.200 100

The electrolyte used for all experiments was 0.5 M HClO₄ prepared from concentrated HClO₄ (double distilled, GFS) and ultrapure water (ELGA, 18 MΩ cm). The gases used (Ar, O₂ and CO) were of the highest commercially available purity (Air Products). Unless stated otherwise, experiments were performed under an atmosphere of argon. Oxygen reduction experiments were performed under an atmosphere of O₂. During potential step measurements, oxygen was bubbled through the electrolyte. Unless otherwise noted, the maximum potential applied to the electrodes was 1.2 V vs. RHE. The screening procedure carried out on each array is outline in Table 1.

EXAMPLE 4: ANATASE AND AMORPHOUS TITANIUM OXIDE

To compare amorphous and crystalline titanium oxide as a support for Pt, separate electrochemical arrays were synthesised. The as-deposited titanium oxide was amorphous. The titanium oxide was crystallised by heating in a tube furnace at 450° C. for 6 hours in the presence of oxygen. XRD confirmed the titanium oxide had been crystallised in the anatase form.

FIG. 4 shows the potential at which 1 μA raw current is reached (threshold value used to measure the ignition or onset potential) during the oxygen reduction slow cycling experiment (i.e. cycling at 20 mV s⁻¹ in oxygenated 0.5 M HClO₄) for various equivalent thicknesses of Pt supported on amorphous and anatase titanium oxide. An ignition or onset potential is defined as the potential at which the absolute value of the current starts to increase from the background (double layer) level in a cyclic voltammetry experiment, indicating that an oxidation or reduction reaction is taking place. Average results were taken across an array row for identical Pt equivalent thicknesses. This provides a measure of the onset potential of the oxygen reduction reaction—the higher the onset potential, the more active the catalyst for the oxygen reduction reaction. It can be seen that at high equivalent thicknesses of Pt, the ignition potential remains fairly constant with decreasing equivalent thickness of Pt. This is similar for both supports.

However, between 5 and 6 ML (monolayers) equivalent thickness of Pt, the ignition potential starts to decrease on both support materials. The effect on the amorphous material is more significant. Under this equivalent thickness for both supports the ignition potential decreases further. On the amorphous titanium oxide at low equivalent thicknesses, there is a large amount of scatter in the data. FIG. 5 shows the potential at which 3 μA raw current is reached in the oxygen reduction slow cycling experiment for the same set of data. At this current it is even clearer that the reduction wave is shifted more significantly negative on the amorphous support. This suggests that the anatase support provides better wetting for the platinum, and therefore higher activity, down to a lower equivalent thickness of Pt.

FIG. 6 shows the voltammetry for one electrode during the oxygen reduction reaction with 0.7 ML equivalent thickness of Pt supported on amorphous titanium oxide. The two currents at which ignition potentials have been measured are indicated by grey lines. Two reduction features are seen, a small feature with a high onset potential and a larger feature with a low onset potential. These two features are probably due to inhomogeneity within the sample, i.e. some large islands of platinum leading to a high ignition potential and some smaller particles leading to the lower ignition potential. The ignition potential measured at 1 μA raw current gives an indication of the onset of the first reduction feature and the ignition potential measured at 3 μA raw current gives an indication of the onset of the second reduction feature.

These results suggest that the platinum shows better wetting on the anatase titanium oxide, allowing bulk platinum like oxygen reduction activity to a lower equivalent thickness.

EXAMPLE 5: ANATASE TUNGSTEN TITANIUM OXIDE

FIG. 7 shows the ignition potentials (potential at which 1 μA raw current is reached) for the second negative cycle of the oxygen reduction slow cycling experiment. Various equivalent thicknesses of Pt were deposited onto anatase TiWO_(x), with varying W content. At low Pt equivalent thicknesses, the arrays containing W had higher ignition potentials (i.e. lower overpotentials). However, by the equivalent thicknesses (˜4.3 ML) where the highest ignition potentials are reached (the lowest overpotentials), all of the samples have similar ignition potentials. This suggests that there is better wetting of the Pt onto the tungsten-doped titanium oxide at low loadings.

As indicated above, atomic percentage values given are on the total metal content. That is to say, 30 at % W indicates 70 at % Ti. The exact stoichiometry including oxygen atoms is undefined but is at or close to stoichiometric, thereby maintains oxide properties.

Use as a Core-Shell Catalyst

The materials described in the present application are readily scaled up from the model thin film samples to bulk core shell powder materials using known techniques, such as those described in US2010/0197490, US2007/0031722, US2009/0117257, US2006/0263675 and CN101455970. Other techniques will be readily apparent to the skilled person. The stability of the materials described is such that they are effective for use in fuel cells.

REFERENCES

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The invention claimed is:
 1. A core-shell catalyst consisting of a core particle and a shell catalyst, wherein said core particle has a diameter of from 10-50 nm and comprises a mixed metal oxide material of tungsten and titanium, wherein the mixed metal oxide material comprises less than 30 atomic % tungsten, calculated on a metals only basis, and wherein said shell catalyst comprises 1 to 20 monolayers of a catalyst material.
 2. The core-shell catalyst of claim 1, wherein the shell catalyst comprises platinum or platinum alloy.
 3. The core-shell catalyst of claim 2, wherein the shell catalyst consists of 1 to 20 monolayers of platinum or platinum alloy.
 4. The core-shell catalyst of claim 3, wherein the shell catalyst consists of 1 to 14 monolayers of platinum or platinum alloy.
 5. The core-shell catalyst of claim 4, wherein the shell catalyst consists of 1 to 6 monolayers of platinum or platinum alloy.
 6. A fuel cell comprising the core-shell catalyst of claim
 5. 7. The core-shell catalyst of claim 2, wherein the mixed metal oxide material comprises less than 15 atomic % tungsten.
 8. The core-shell catalyst of claim 7, wherein said core particle consists of said mixed metal oxide.
 9. The core-shell catalyst of claim 8, wherein the shell catalyst consists of 1 to 14 monolayers of platinum or platinum alloy.
 10. The core-shell catalyst of claim 9, wherein the shell catalyst consists of 1 to 6 monolayers of platinum or platinum alloy.
 11. A fuel cell comprising the core-shell catalyst of claim
 10. 12. The core-shell catalyst of claim 7, wherein the mixed metal oxide material comprises from 6 to 11 atomic % tungsten.
 13. The core-shell catalyst of claim 12, wherein said core particle consists of said mixed metal oxide.
 14. The core-shell catalyst of claim 13, wherein the shell catalyst consists of 1 to 14 monolayers of platinum or platinum alloy.
 15. The core-shell catalyst of claim 14, wherein the shell catalyst consists of 1 to 6 monolayers of platinum or platinum alloy.
 16. A fuel cell comprising the core-shell catalyst of claim
 15. 17. The core-shell catalyst of claim 12, wherein the mixed metal oxide material comprises from 7 to 9 atomic % tungsten.
 18. The core-shell catalyst of claim 17, wherein said core particle consists of said mixed metal oxide.
 19. The core-shell catalyst of claim 18, wherein the shell catalyst consists of 1 to 14 monolayers of platinum or platinum alloy.
 20. The core-shell catalyst of claim 19, wherein the shell catalyst consists of 1 to 6 monolayers of platinum or platinum alloy.
 21. A fuel cell comprising the core-shell catalyst of claim
 20. 22. The core-shell catalyst of claim 1, wherein the titanium oxide is in a crystalline form.
 23. The core-shell catalyst of claim 22, wherein the crystalline titanium oxide is anatase titanium oxide.
 24. A fuel cell comprising the core-shell catalyst of claim
 1. 25. A method of producing a core-shell catalyst, the method comprising: forming a core particle having a diameter of from 10-50 nm and comprising a mixed metal oxide material of tungsten and titanium, wherein the material comprises less than 30 atomic % tungsten, calculated on a metals only basis; and forming a catalytic shell layer comprising 1 to 20 monolayers of a catalyst material on the core particle.
 26. The method of claim 25, wherein the mixed metal oxide material comprises less than approximately 15 atomic % tungsten.
 27. The method of claim 26, wherein the mixed metal oxide material comprises from 6 to 11 atomic % tungsten.
 28. The method of claim 27, wherein the mixed metal oxide material comprises from 7 to 9 atomic % tungsten.
 29. The method of claim 28, wherein the shell layer consists of 1 to 14 monolayers of platinum or platinum alloy.
 30. The method of claim 29, wherein the shell layer consists of 1 to 6 monolayers of platinum or platinum alloy.
 31. The method of claim 27, wherein the shell layer consists of 1 to 14 monolayers of platinum or platinum alloy.
 32. The method of claim 31, wherein the shell layer consists of 1 to 6 monolayers of platinum or platinum alloy.
 33. The method of claim 25, wherein the shell layer consists of 1 to 20 monolayers of platinum or platinum alloy.
 34. The method of claim 33, wherein the shell layer consists of 1 to 14 monolayers of platinum or platinum alloy.
 35. The method of claim 34, wherein the shell layer consists of 1 to 6 monolayers of platinum or platinum alloy.
 36. The method of claim 25, wherein the titanium oxide is anatase titanium oxide.
 37. The method of claim 26, wherein the shell layer consists of 1 to 14 monolayers of platinum or platinum alloy.
 38. The method of claim 37, wherein the shell layer consists of 1 to 6 monolayers of platinum or platinum alloy. 